JPH055012A - Nonaqueous fluorinated resin and coating consisting essentially of the same - Google Patents

Abstract

PURPOSE:To obtain the subject new resin which is a fluorinated resin, good in solubility in organic solvents and compatibility with curing agents, excellent in weather resistance of films and capable of providing fluorine-based coating improved in affinity for pigments and adhesion to substrates. CONSTITUTION:A nonaqueous fluorinated resin, containing fluorine in the molecule and further hydroxyl groups and quaternary onium groups through ether bonds in side chains and having 500-100000 number-average molecular weight with 0.01-40wt.% quaternary onium salt content. The aforementioned resin is obtained by, e.g. reacting an epoxy group-containing fluorinated resin with an onium salt-forming substance such as diethylamine in combination with an acid. The epoxy group-containing fluorinated resin which is a raw material is obtained by, e.g. copolymerizing monomer materials consisting essentially of epoxy group-containing allyl ethers such as glycidyl ether and a fluorinated vinyl monomer such as chlorotrifluoroethylene.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel non-aqueous fluorine-containing resin and a paint containing the same as a main component.

[0002]

Fluorine-containing resins have hitherto been widely used in many fields because of their excellent heat resistance, mechanical properties, chemical resistance, weather resistance and the like. One of its uses is as a coating film forming component of paint.
For example, a fluororesin paint using a tetrafluoroethylene polymer or a vinylidene fluoride polymer is known,
Since it has excellent lubricity, non-adhesiveness, weather resistance and chemical resistance, it is used as a coating material in the fields of chemical industry, food, construction, machinery and the like. However, the fluororesin coating composition has a drawback that it needs to be baked at a high temperature and the range of use is inevitable. Therefore, in recent years, it is soluble in an organic solvent and can be cured at room temperature. Attempts have been made to develop solvent-based paints using fluorine-containing resins having reactive groups.

Incidentally, examples of the fluorine-containing resin soluble in an organic solvent include, for example, JP-A-57-34107, JP-A-61-275311, JP-A-61-57609, and JP-A-62-174213. Japanese Patent Laid-Open No. 63-182312
Copolymers of fluoroolefins and vinyl monomers copolymerizable therewith, which are found in Japanese Unexamined Patent Publication No. 2003-242, are known. However, in these copolymers, it is still necessary to improve the dispersibility depending on the type of pigment or the like used in combination when used as a paint base, and to improve the adhesion to the base material depending on the usage form.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a non-aqueous fluorine-containing resin in which the above-mentioned problems of the prior art have been solved, that is, a fluorine-containing resin having good solubility in an organic solvent and compatibility with a curing agent, and The purpose of the present invention is to provide a fluorine-based coating composition containing this as a main component and having excellent weather resistance, and having improved affinity with pigments and the like and adhesion with a substrate.

[0005]

Means for Solving the Problems As a result of intensive studies in view of the above points, the present inventors have found that the above problems can be solved by introducing a functional group having a specific structure into a fluororesin. The present invention has been completed and the present invention has been completed. That is, the present invention is: a number average molecular weight of 500 to 100,000 containing a fluorine group in a molecule and a hydroxyl group through an ether bond in a side chain and a fourth onium salt, and a fourth onium salt content. A non-aqueous fluorine-containing resin of 0.01 to 40% by weight is provided, and a fluorine-containing resin comprising the following constituents, and a fluorine-based coating material containing the fluorine-containing resin as a main component.

The present invention will be described in detail below. The non-aqueous fluororesin according to the present invention has the following (a) or
It can be manufactured by the method (b). (A) An epoxy group-containing fluororesin and an onium salt-forming substance are combined and reacted with an organic acid or an inorganic acid. (B) A vinyl monomer obtained by reacting an epoxy group-containing vinyl monomer with an onium salt-forming substance in combination with an organic acid or an inorganic acid, and a monomer mixture containing a fluorine-containing vinyl monomer as an essential component. Copolymerize.

As the method for producing the non-aqueous fluorine-containing resin of the present invention, the above method (a) or (b) can be arbitrarily selected. First, a method of reacting (a) an epoxy group-containing fluororesin and an onium salt-forming substance in combination with an organic acid or an inorganic acid will be described. In this case, in the non-aqueous fluororesin of the present invention, examples of the epoxy group-containing fluororesin to be the starting material include those having the following (a) and (b) as essential constituent components. Formula (a):

[0008]

[Chemical 1]

20 to 70 mol% of a structural unit represented by the formula (b):

[0010]

[Chemical 2]

The structural unit represented by 0.01 to 40 mol%
In the non-aqueous fluorine-containing resin of the present invention, the epoxy group-containing fluorine-containing resin having the above-mentioned (a) and (b) as essential starting components to be a starting material is copolymerized with a corresponding vinyl monomer. Obtained by That is, as a specific example of the fluorine-containing vinyl monomer corresponding to (a), CH ₂
= CF ₂ , CHF = CF ₂ , CHCl = CF ₂ , CFC
l = CF ₂ , CF ₂ = CF ₂ , CF ₃ CF = CF ₂ , C
F ₃ CH = CF ₂ , CCl ₂ = CF ₂ , CF ₃ CCl =
CF _2, (CF ₃₎ can be exemplified fluoroolefin such as ₂ C = CF _2, particularly tetrafluoroethylene (CF ₂ = CF _2), chlorotrifluoroethylene (CF ₂ = CFCl) and hexafluoropropene ( C
F ₂ = CFCF ₃ ) is preferred. These fluoroolefins may be used alone or in combination of two or more.

Specific examples of the vinyl monomer corresponding to (b) include:

[0013]

[Chemical 3]

Epoxy group-containing vinyl ethers such as;

[0015]

[Chemical 4]

Examples thereof include epoxy group-containing allyl ethers and the like. Each of these may be used alone,
You may use it in combination of 2 or more type. In the non-aqueous fluorine-containing resin of the present invention, the epoxy group-containing fluorine-containing resin to be the starting material is, in addition to the constituent components of (a) and (b), within the range of not more than 50 mol% (c).
It is preferable to contain a copolymerized unit of a hydroxyl group-containing vinyl monomer and / or (d) a copolymerized unit of another vinyl monomer.

Specific examples of the hydroxyl group-containing vinyl monomer forming the unit (c) include 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether,
Hydroxyalkyl vinyl ethers such as 4-hydroxycyclohexyl vinyl ether, 2-hydroxyallyl vinyl ether, hydroxyalkyl allyl ethers such as 4-hydroxybutyl allyl ether, 2-hydroxyethyl (meth) acrylate, 4-hydroxypropyl (meth) acrylate, etc. Hydroxyl group-containing (meth) acrylates of 2-hydroxyethyl crotonate, 4
Typical examples are hydroxyl group-containing crotonic acid esters such as hydroxypropyl crotonate, allyl alcohol, and the like. Among these, hydroxyalkyl vinyl ethers are preferable because of their good reactivity with fluoroolefins. These hydroxyl group-containing vinyl monomers may be used alone or in combination of two or more.

Specific examples of the vinyl monomer forming the unit (d) include olefins such as ethylene, propylene and isobutylene, haloolefins such as vinyl chloride and vinylidene chloride, vinyl acetate, n-butyrate vinyl, and the like. Vinyl benzoate, vinyl p-t-butyl benzoate, vinyl pivalate, vinyl 2-ethylhexanoate, vinyl versatate, vinyl laurate, and other carboxylic acid vinyl esters, isopropenyl acetate, isopropenyl propionate, and other carboxylic acid vinyl esters. Acid isopropenyl esters, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, neopentyl vinyl ether, 2
-Chain alkyl vinyl ethers such as ethylhexyl vinyl ether and octyl vinyl ether, fluorovinyl ethers such as pentafluoroethyl vinyl ether and 2-perfluorooctyl ethyl vinyl ether, cycloalkyl vinyl ethers such as cyclopentyl vinyl ether and cyclohexyl vinyl ether, aryl vinyl ethers such as phenyl vinyl ether , Aralkyl vinyl ethers such as benzyl vinyl ether and phenethyl vinyl ether, vinyl-9-aza-3-ethyl-8,8,9,10,10-pentamethyl-1,5-
Dioxaspiro [5,5] -3-undecyl methyl ether, vinyl-9-aza-3-ethyl-8,8,10,
10-Tetramethyl-1,5-dioxaspiro [5,5
5] -3-Piperidinyl group-containing vinyl ethers such as undecyl methyl ether, aromatic vinyl compounds such as styrene and vinyltoluene Allyl formate, allyl acetate, allyl butyrate, allyl benzoate, allyl cyclohexanecarboxylate, allyl cyclohexylpropionate, 4-allyloxy-2,2,6,6, -tetramethylpiperidine, 4
-Allyloxy-1,2,2,6,6, -allyl esters such as pentamethylpiperidine, allyl ethers such as allyl ethyl ether and allyl phenyl ether, butyl (meth) acrylate, methyl (meth) acrylate, cyclohexyl ( (Meth) acrylate, isobornyl (meth) acrylate, 2-hydroxy-4- (2-
Methacryloxyethoxy) benzophenone, 4- (meth) acryloyloxy-2,2,6,6, -tetramethylpiperidine, 4- (meth) acryloyloxy-
1,2,2,6,6-pentamethylpiperidine, perfluoromethyl (meth) acrylate, perfluoropropyl (meth) acrylate, perfluoropropylomethyl (meth) acrylate, perfluoromethylmethyl (meth) acrylate, Acrylic acid and methacrylic acid esters such as 2-perfluorooctylethyl (meth) acrylate and perfluoroisononylmethyl (meth) acrylate, acrylamides such as acrylamide and N-methylolacrylamide, and Japanese Patent Application No. 1-23712.
As shown in No. 2, a vinyl monomer having a cyclic hydrocarbon group introduced through a urethane bond, Japanese Patent Application No. 2-10.
Examples of the endocyclic vinyl ethers shown in 1695.

Among these, vinyl monomers having a cyclic hydrocarbon group introduced through a urethane bond, which are shown in Japanese Patent Application No. 1-237122, and Japanese Patent Application No. 2-101695. Fluorine-containing resins using cyclic vinyl ethers are preferable because they have excellent compatibility with a curing agent, hardness, and gloss. These vinyl monomers may be used alone or in combination of two or more.

In the non-aqueous fluororesin of the present invention, the epoxy group-containing fluororesin to be the starting material corresponds to the above formulas (a) and (b) in the presence or absence of a solvent. It can be produced by copolymerizing a predetermined proportion of a vinyl monomer mixture containing a vinyl monomer as an essential component, using a polymerization initiator, ionizing radiation, or the like as a polymerization initiation source.

As the polymerization initiator, a water-soluble one or an oil-soluble one is appropriately used depending on the type of polymerization or desired. Examples of the oil-soluble initiator include azo compounds such as azobisisobutyronitrile and 2,2′-azobis- (2,4-dimethylvaleronitrile), t-butylperoxypivalate and t-butylperoxyiso. Peroxyester type peroxides such as butyrate, diacyl peroxide type peroxides such as octanoyl peroxide and lauroyl peroxide, dialkyl peroxydicarbonate type peroxides such as diisopropyl peroxydicarbonate, benzoyl peroxide And dialkyl peroxide type peroxides.

As the water-soluble polymerization initiator, for example, a persulfate such as potassium persulfate, hydrogen peroxide, or a redox initiator comprising a combination of these with a reducing agent such as sodium bisulfite and sodium thiosulfate, and further ,
Inorganic initiators such as those in which a small amount of iron, ferrous salt, silver nitrate, etc. coexist, dibasic acid peroxides such as disuccinic acid peroxide, diglutaric acid peroxide, and monosuccinic acid peroxide, azobi Organic initiators such as perisobutylamidine dibasic acid salts are mentioned. The amount of these polymerization initiators to be used is appropriately selected depending on the type, copolymerization reaction conditions, etc., but 0.005 to 5% by weight, preferably 0.05 to the total amount of the monomers usually used. To 0.5% by weight.

The polymerization method is not particularly limited and, for example, a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, a solution polymerization method and the like can be used. From the viewpoint of stability of the polymerization reaction operation, etc. Solvents such as lower alkyl-substituted benzenes such as xylene and toluene, esters such as butyl acetate, ketones such as methyl isobutyl ketone, alcohols such as t-butanol, and saturated halogenated hydrocarbons having one or more fluorine atoms are used as a solvent. The solution polymerization method, the emulsion polymerization method in an aqueous medium, and the bulk polymerization method that does not require separation from the solvent are preferably used.

In the case of copolymerization in an aqueous medium, a suspension agent or an emulsifier is usually used as a dispersion stabilizer, and a basic buffer is added to adjust the pH value of the reaction solution during polymerization to 4, preferably. It is desirable to set it to 6 or more. Also in the case of the solution polymerization method and the bulk polymerization method, addition of a basic substance such as potassium carbonate or an amine compound is effective. Further, the polymerization system is not particularly limited, and any of batch system, semi-continuous system and continuous system can be used.

The reaction temperature in the copolymerization reaction is usually −
Within the range of 30 to + 150 ° C, it is appropriately selected depending on the type of the polymerization initiation source and the polymerization medium, and is usually 0 to 100 ° C, preferably 10 to 90 ° C. The reaction pressure is not particularly limited, but it is selected within the range of normal pressure to 100 kg / cm ² . Further, the copolymerization reaction can be carried out by adding an appropriate chain transfer agent.

The molecular weight of the epoxy group-containing fluororesin thus obtained was determined by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent and monodisperse polystyrene of known molecular weight as a standard substance. The molecular weight (Mn) is 500 to 100,
000, preferably 1,000 to 50,000, the epoxy group content is 0.01 to 40% by weight, the glass transition temperature (Tg) is usually -50 to 120 ° C, preferably -10 to 100 ° C. Is.

Subsequently, the epoxy group of the obtained epoxy group-containing fluororesin is reacted with an onium salt-forming substance in combination with an organic acid or an inorganic acid to give a fourth compound.
A non-aqueous fluororesin containing an onium salt is obtained. The onium salt-forming substance, a basic amino compound,
Examples thereof include tertiary phosphine and secondary sulfide, which can generate quaternary ammonium, phosphonium and sulfonium bases, respectively.

Examples of the basic amino compound include primary amines, secondary amines, tertiary amines, polyamines,
Any of alkanolamines may be used. Specific examples of these basic amino compounds include, for example, diethylamine, dipropylamine, N-methylethanolamine, diethanolamine, ethylenediamine, diethylenetriamine, dimethylcyclohexylamine, dimethylethanolamine, triethanolamine, triethylamine, pyrrolidine, piperidine, morpholine and the like. Is mentioned. When a polyamine such as diethylenetriamine is used, its primary amino group is preferably a ketimine derivative obtained by previously reacting it with a ketone such as acetone, methyl ethyl ketone or methyl isobutyl ketone.

As the third phosphine, virtually any phosphine which does not contain an interfering group can be used. Specific examples of these third phosphines include trimethylphosphine, triethylphosphine, tributylphosphine, dimethylphosphine, diethylphosphine, phenyldiethylphosphine, diphenylmethylphosphine, triphenylphosphine, tribenzylphosphine, tetramethylenemethylphosphine, and the like. ..

The second sulfide can be virtually any sulfide that reacts with an epoxy group and does not contain an interfering group. Specific examples of these sulfides include, for example, diethyl sulfide, dipropyl sulfide,
Examples thereof include dibutyl sulfide, dihexyl sulfide, diphenyl sulfide, ethylphenyl sulfide, tetramethylene sulfide, pentamethylene sulfide, thiodiethanol, thiodipropanol and thiodibutanol.

The onium salt-forming substances may be used alone or in combination of two or more.
The amount used is 0.2 to 2.0 equivalents, preferably 0.5 to 1.2 equivalents, based on the epoxy groups of the epoxy group-containing fluororesin. Examples of the organic acid include formic acid, acetic acid, lactic acid, propionic acid, oxalic acid, acrylic acid, methacrylic acid, p-toluenesulfonic acid, and the like.
Examples of the inorganic acid include boric acid, hydrochloric acid, sulfuric acid, phosphoric acid and the like.

The amount of these acids used is 0.2 to 5 equivalents, preferably 0.5 to 5 equivalents, relative to the onium salt-forming substance.
It is 1.5 equivalents. The reaction of the epoxy group-containing fluororesin with the onium salt-forming substance and the organic acid or inorganic acid is usually carried out by reacting a mixture of the onium salt-forming substance and an organic acid or inorganic acid with the epoxy group-containing fluororesin. The primary amines and secondary amines having active hydrogen may be reacted with an epoxy group-containing fluororesin in advance and then neutralized with an organic acid or an inorganic acid.

The reaction of the epoxy group-containing fluororesin with the onium salt-forming substance and the organic or inorganic acid is about 2
This can be achieved by heating at 0 ° C to 200 ° C, preferably 50 to 150 ° C for about 1 to 5 hours. The reaction is
It is usually carried out in a suitable organic solvent. Examples of the organic solvent include aromatic hydrocarbons such as toluene and xylene,
Alcohols such as n-butanol, ethyl acetate, acetic acid n
Examples thereof include esters such as butyl, ketones such as methyl ethyl ketone and methyl isobutyl ketone, glycol ethers such as ethyl cellosolve, and various commercially available thinners.

The amount of the organic solvent used depends on the fluorine-containing resin group.
Use 10-100 parts by weight per 100 parts by weight of product
Is preferred. Subsequently, the above (b) (epoxy group-containing vinyl
Organic monomer or onium salt-forming substance
Vinyl monomer and fluorine-containing vinyl reacted with acid
Copolymerize a monomer mixture containing nyl monomer as an essential component
How to do this is explained. In this case, the non-aqueous system of the present invention is included.
The fluororesin is a fluorine-containing vinyl monomer (20 to 70 mol).
%), Onium salt-forming substance and epoxy group-containing vinyl
React with a monomer in combination with an organic or inorganic acid
Vinyl monomer (0.01-40 mol%)
As a copolymerization component, if necessary, hydroxyl group-containing vinyl monomer
(0 to 50 mol%) and / or other vinyl monomer
(0 to 50 mol%) is the epoxy in the above method (a)
Copolymerize in the same manner as in the production of group-containing fluororesin
Can be obtained by

Specific examples of the above-mentioned fluorine-containing vinyl monomer, epoxy group-containing vinyl monomer, onium salt-forming substance, organic acid, inorganic acid, hydroxyl group-containing vinyl monomer, and other vinyl monomers Examples of the same include those similar to the above-mentioned method (a). Further, regarding the method of reacting the onium salt-forming substance and the epoxy group-containing vinyl monomer in combination with an organic acid or an inorganic acid, the onium salt-forming substance and the epoxy group-containing fluororesin in the method (a) are also used. It is based on the method of reacting in combination with an organic acid or an inorganic acid.

The non-aqueous fluorine-containing resin obtained by the above-mentioned method (a) or (b) has the following formula (a):
And at least one of the formulas (e), (f), and (g) is an essential constituent unit, and the molecular weight thereof is 500 to 100,000, preferably 1,000 to 5 in terms of number average molecular weight.
The content of the fourth onium salt is 0.0
1-40% by weight, fluorine content 5-70% by weight, Tg
The (glass transition temperature) is usually -50 to 120 ° C, preferably -20 to 100 ° C. Formula (a):

[0037]

[Chemical 5]

(E) Formula: When the onium salt-forming substance is a basic amino compound,

[0039]

[Chemical 6]

Formula (f): When the onium salt-forming substance is a third phosphine,

[0041]

[Chemical 7]

Formula (g): When the onium salt-forming substance is the second sulfide,

[0043]

[Chemical 8]

The fluorine-containing resin of the present invention having such a composition, molecular weight, and glass transition temperature is soluble in an organic solvent, excellent in compatibility with a curing agent and excellent in affinity with a pigment and the like. A cured coating film of a coating material containing a fluororesin as a main component has gloss and hardness and excellent weather resistance. In the non-aqueous fluorine-containing resin of the present invention, when the epoxy group-containing fluorine-containing resin or the epoxy group-containing vinyl monomer and the onium salt-forming substance are reacted under an epoxy group excess condition, the fluorine-containing resin is a cured site. As a curing agent, a polyaddition type curing agent such as polyamines, acid anhydrides, polyphenols and polymercaptans, or a catalyst type curing agent such as imidazoles and BF ₃ is used as a curing agent. It can be heat-cured or room-temperature cured.

Further, in the non-aqueous fluorine-containing resin of the present invention, a unit which also contains a unit obtained by copolymerizing a vinyl monomer having a hydroxyl group as a constituent component has a hydroxyl group as a curing site, and is a usual thermosetting acrylic resin. Curing agents used in paints, such as polyvalent isocyanates, block isocyanate curing agents, melamine curing agents, urea resin curing agents,
It can be cured by heating using a polybasic acid curing agent or the like.

Further, the hydroxyl group-containing fluororesin can be cured at room temperature by using polyisocyanates. As the polyvalent isocyanates,
For example, non-yellowing diisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate and adducts thereof, polyvalent isocyanates having an isocyanurate ring, and the like are preferably mentioned. A polyvalent isocyanate having an isocyanurate ring with good solubility is suitable. When using these polyvalent isocyanates for room temperature curing, a known catalyst such as dibutyltin dilaurate may be added to accelerate curing.

Further, the non-aqueous fluorine-containing resin of the present invention can be used as a lacquer type coating material when it does not contain the above curing unit. The present invention provides the above-mentioned novel non-aqueous fluorine-containing resin, and a fluorine-based coating material containing this as a main component, and various solvents are used in preparing the fluorine-containing resin as a solution type coating material. be able to.

Examples of the solvent include aromatic hydrocarbons such as toluene and xylene, alcohols such as n-butanol, esters such as n-butyl acetate, ketones such as methyl isobutyl ketone, glycols such as ethyl cellosolve. Examples thereof include ethers and various commercially available thinners. The solution-type paint is prepared by homogenizing the fluorine-containing resin and the solvent by using a mixing machine which is usually used for preparing a paint, such as a ball mill, a paint shaker, a sand mill, a jet mill, a three-roll mill and a kneader. It can be carried out by mixing. At this time, if desired,
A pigment, a dispersion stabilizer, a viscosity modifier, a leveling agent, an anti-gelling agent, an ultraviolet absorber and the like can be added.

[0049]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples.
The present invention is not limited to the embodiments. Molecular weights of various resins: Determined from a polystyrene standard calibration curve using gel permeation chromatography.

(Device used) Device: Shimadzu LC-
3A column: Tosoh Corporation TSKgel G-5000 HXL TSKgel G-4000 HXL TSKgel G-2000 HXL Detector: Shimadzu RID-6A Data processing: Shimadzu C-R4A Carrier: Tetrahydrofuran Hydroxyl value; JIS K-0070 Was measured. Epoxy value; measured according to ASTM-D1652. Gloss, Flexibility, Adhesion (Al); JIS K-540
It measured according to 0. Weather resistance: Determined according to ASTM G-53.

[0051]

Example 1 A stainless steel autoclave with an internal volume of 1 liter equipped with a stirrer was charged with 7.7 g of potassium carbonate, and the inside of the autoclave was replaced with nitrogen gas three times. Next, 7 g of glycidyl allyl ether, 23 g of 4-hydroxybutyl vinyl ether, 14 g of 2.3-dihydrofuran, 14 g of ethyl vinyl ether, 34 g of isobutyl vinyl ether, and 117 chlorotrifluoroethylene.
g, 209 g of butyl acetate and 1.7 g of t-butyl peroxypivalate as an initiator were charged, and polymerization was carried out at 67 ° C. for 8 hours. After completion of the polymerization, unreacted chlorotrifluoroethylene was removed, the autoclave was opened, and the produced fluororesin solution was taken out. After potassium carbonate was removed from this fluororesin solution by filtration, it was reprecipitated with n-hexane and dried. The yield of fluororesin is 197
It was g.

The number average molecular weight of the obtained fluorine-containing resin was 9,800, the fluorine content was 27.3%, the hydroxyl value was 54 mgKOH / g, and the epoxy value was 0.28 mmol.
It was / g. This is designated as resin A. Resin A 50g
Was dissolved in 50 g of butyl acetate, 1.7 g of thiodiethanol and 0.8 g of acetic acid were added, and the mixture was reacted at 80 ° C. for 2 hours to obtain a nonaqueous fluorine-containing resin solution having a nonvolatile content (NV) of 50.7%. .. The number average molecular weight of the obtained non-aqueous fluororesin was 10,600.

[0053]

Example 2 The reaction was carried out in the same manner as in Example 1 except that 1.7 g of thiodiethanol was replaced with 1.4 g of triethylamine and 0.8 g of acetic acid was replaced with 1.3 g of lactic acid. An aqueous fluororesin solution was obtained. The number average molecular weight of the obtained non-aqueous fluororesin was 10,300.

[0054]

Example 3 A nonaqueous fluorine-containing resin solution having a nonvolatile content of 51.3% was obtained by carrying out the reaction in the same manner as in Example 1 except that 1.7 g of thiodiethanol was replaced with 3.6 g of triphenylphosphine. The number average molecular weight of the obtained non-aqueous fluororesin was 11,300.

[0055]

Example 4 100 g of glycidyl vinyl ether was dissolved in 282 g of butyl acetate, and then thiodiethanol 1 was added.
22 g and 60 g of acetic acid were added and reacted at 50 ° C. for 2 hours. This is referred to as a monomer A solution. Subsequently, 7.7 g of potassium carbonate was charged into an autoclave with a stirrer made of stainless steel and having an internal volume of 1 liter, and the inside of the autoclave was replaced with nitrogen gas three times, and then the monomer A solution 34
g, 4-hydroxybutyl vinyl ether 23 g, 2.
21 g of 3-dihydrofuran, 44 g of isobutyl vinyl ether, 117 g of chlorotrifluoroethylene, 205 g of butyl acetate and 1.7 g of t-butylperoxypivalate as an initiator were charged, and polymerization was carried out at 67 ° C. for 8 hours. After completion of the polymerization, unreacted chlorotrifluoroethylene was removed, the autoclave was opened, and the produced fluororesin solution was taken out. After potassium carbonate was removed from this fluororesin solution by filtration, it was reprecipitated with n-hexane and dried. The yield of the fluororesin was 207 g.

The number average molecular weight of the obtained fluororesin is 1
It was 0,400, the fluorine content was 25.8%, and the hydroxyl value was 52 mgKOH / g.

[0057]

Example 5 An autoclave with an internal volume of 1 liter and made of a stainless steel and equipped with a stirrer was charged with 7.7 g of potassium carbonate, and the inside of the autoclave was replaced with nitrogen gas three times. Next, 23 g of 4-hydroxybutyl vinyl ether, 25 g of cyclohexyl isocyanate, 50 g of isobutyl vinyl ether, and 98 g of xylene were charged and the mixture was heated at 80 ° C. for 6 hours.
Reacted for hours. Then glycidyl vinyl ether 3
0 g, 117 g of chlorotrifluoroethylene, 147 g of xylene and 2.8 g of octanoyl peroxide as an initiator were charged, and polymerization was carried out at 73 ° C. for 8 hours. After completion of the polymerization, unreacted chlorotrifluoroethylene was removed, the autoclave was opened, and the produced fluororesin solution was taken out. After potassium carbonate was removed from this fluororesin solution by filtration, it was reprecipitated with n-hexane and dried. The yield of the fluororesin was 238 g.

The number average molecular weight of the obtained fluororesin is 1
It was 1,400, the fluorine content was 22.8%, and the epoxy value was 1.23 mmol / g. This is referred to as resin B. After dissolving 50 g of this resin B in 50 g of xylene, 1.0 g of diethyl sulfide and 0.4 g of hydrochloric acid were added to give 5
The reaction was carried out at 0 ° C. for 1 hour to obtain a non-aqueous fluororesin solution having a nonvolatile content (NV) of 50.3%. The number average molecular weight of the obtained non-aqueous fluororesin was 12,100.

[0059]

Example 6 The same procedure as in Example 5 was repeated except that 1.0 g of diethyl sulfide was replaced with 1.5 g of dibutylamine, and 0.4 g of hydrochloric acid was replaced with 0.7 g of acetic acid.
A 0.6% non-aqueous fluororesin solution was obtained. The number average molecular weight of the obtained non-aqueous fluororesin was 10,300.

[0060]

Examples 7 to 10 The fluororesin solutions obtained in Examples 1 to 3 and the fluororesins obtained in Example 4 adjusted to a solid content of 50% with xylene were used as main components, and a curing agent was used. As "Duranate TPA" (Asahi Kasei Corporation)
(Manufactured by Mitsui Chemicals Co., Ltd.) was mixed with each other so that NCO / OH = 1/1, and then xylene was used as a thinner for Ford Cup # 4.
The coating time was adjusted to 15 seconds. The coating film obtained is 1
After baking at 20 ° C. for 1 hour, the coating film appearance, coating film gloss, flexibility, adhesiveness (Al), and weather resistance were evaluated.

Each of the fluororesin solutions obtained in Examples 1 to 3 and the fluororesins obtained in Example 4 adjusted to a solid content of 50% with xylene and various pigments (quinacridone red and Carbon black) and a predetermined pigment weight concentration (quinacridone red; PWC = 12%, carbon black; PWC = 5%),
The main components were those dispersed for 2 hours using a sand mill, compounded and coated as described above, and the dispersibility of the pigment was evaluated by visually observing the gloss and the degree of aggregation of the pigment.

The results are shown in Table 1.

[0063]

[Examples 11 to 12] 100 g of each fluororesin solution obtained in Examples 5 to 6 was used as the main agent, and 2% as the curing agent.
After blending 2 g of ethyl-4-methylimidazole into each, 1 with Ford Cup # 4 using xylene as a thinner.
It was adjusted to 5 seconds and painted. The obtained coating film is 120
After baking at 0 ° C. for 1 hour, the coating film physical properties were evaluated in the same manner as in Examples 7-10.

Further, each of the fluorine-containing resin solutions obtained in Examples 5 to 6 and various pigments were blended so as to have a predetermined pigment weight concentration, and dispersed for 2 hours using a sand mill, each of which was used as a main agent. As described above, the composition and coating were performed, the gloss and the degree of aggregation of the pigment were visually determined, and the pigment dispersibility was evaluated in the same manner as in Examples 7 to 10. Each result is shown in Table 1.
Shown in.

[0065]

Comparative Example 1 7.7 g of potassium carbonate was charged into a stainless steel autoclave equipped with a stirrer having an internal volume of 1 liter, and the inside of the autoclave was replaced with nitrogen gas three times. Then, 23 g of 4-hydroxybutyl vinyl ether,
14 g of 2.3-dihydrofuran, 14 g of ethyl vinyl ether, 40 g of isobutyl vinyl ether, 117 g of chlorotrifluoroethylene, 208 g of xylene and 1.7 g of t-butylperoxypivalate as an initiator were charged, and polymerization was carried out at 67 ° C. for 8 hours. .. After completion of the polymerization, unreacted chlorotrifluoroethylene was removed, the autoclave was opened, and the produced copolymer solution was taken out. After removing potassium carbonate by filtration from the copolymer solution,
It was reprecipitated with n-hexane and dried. The yield of the copolymer was 201 g.

The number average molecular weight of the obtained copolymer was 10,
100, fluorine content 27.4%, hydroxyl value 5
It was 4 mg KOH / g.

[0067]

[Comparative Examples 2 to 3] The fluororesin and the resin A obtained in Comparative Example 1 each having a solid content of 50% adjusted with xylene were used as main components, and "Duranate TPA" (manufactured by Asahi Kasei Kogyo Co., Ltd.) as a curing agent. ) Was mixed with each other so that NCO / OH = 1/1, and the coating was performed by adjusting the Ford cup # 4 for 15 seconds with xylene as a thinner. The obtained coating film was baked at 120 ° C. for 1 hour, and then the coating film appearance, coating film gloss, flexibility, adhesiveness (A), and weather resistance were evaluated.

Further, the fluorine-containing resin obtained in Comparative Example 1,
And resin A with xylene adjusted to a solid content of 50% and various pigments (quinacridone red and carbon black)
And a predetermined pigment weight concentration (quinacridone red; PWC
= 12%, carbon black; PWC = 5%) and dispersed for 2 hours using a sand mill as the main agent. Blend and paint as described above to determine the degree of aggregation of gloss and pigment. It was visually determined and the pigment dispersibility was evaluated. The respective results are shown in Table 1.

[0069]

Comparative Example 4 100 g of a fluorine-containing resin solution prepared by adjusting the resin B to a solid content of 50% with xylene was used as a main component, and 2 g of 2-ethyl-4-methylimidazole was added as a curing agent, and then xylene was used as a thinner. Cup # 4
The coating time was adjusted to 15 seconds. The coating film obtained is 1
After baking at 20 ° C. for 1 hour, the coating film physical properties were evaluated in the same manner as in Comparative Examples 2 to 3.

The resin B was mixed with xylene to a fluorine-containing resin solution adjusted to a solid content of 50%, and various pigments were mixed so as to have a predetermined pigment weight concentration, and then dispersed using a sand mill for 2 hours. Then, the composition and coating were performed as described above, the gloss and the degree of aggregation of the pigment were visually determined, and the pigment dispersibility was evaluated in the same manner as in Comparative Examples 2 and 3. The respective results are shown in Table 1.

[0071]

[Table 1]

[0072]

As is apparent from the above results, according to the present invention, it is soluble in an organic solvent, has excellent compatibility with a curing agent, and has excellent affinity with various fillers such as pigments and reinforcing agents. A non-aqueous fluorine-containing resin that can be cured at room temperature can be easily provided. Further, the fluorine-based coating material of the present invention containing the fluorine-containing resin as a main component can give a coating film which is glossy and hard, and which has excellent adhesion to a substrate and excellent weather resistance under mild conditions. For example, it is useful as a baking paint for a colored rigid plate, a colored aluminum plate, an aluminum sash, or as a normally dry type paint that can be applied on site.

Further, regarding the material of the base material, in addition to metallic materials, inorganic materials such as glass and concrete, FRP,
It is preferably used for coating plastics such as polyethylene, polypropylene, ethylene-vinyl acetate copolymer, polyvinyl chloride and polyvinylidene chloride, and organic materials such as wood. Further, the fluorine-based paint is also useful in specific applications such as automobile top coats, exterior colored glass, and cement roof tiles.

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Claims (1)

Claims: 1. A number-average molecular weight of 500 to 100,000, which contains fluorine in the molecule and contains a hydroxyl group through an ether bond in the side chain and a quaternary onium salt.
A non-aqueous fluorine-containing resin having a fourth onium salt content of 0.01 to 40% by weight. 2. A coating material containing the non-aqueous fluorine-containing resin according to claim 1 as a main component.